Process for preparation of functionalized ethylene and propylene copolymer

ABSTRACT

The present invention relates to a process for the manufacture of a functionalized ethylene and propylene copolymer composition. The invention further relates to such functionalized ethylene and propylene copolymer composition.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage application of PCT/EP2018/086852,filed Dec. 24, 2018, which claims the benefit of European ApplicationNo. 17210400.2, filed Dec. 22, 2017, European Application No.17210412.7, filed Dec. 22, 2017, European Application No. 17210434.1,filed Dec. 22, 2017, European Application No. 17210485.3, filed Dec. 22,2017, European Application No. 17210447.3, filed Dec. 22, 2017, andEuropean Application No. 17210534.8, filed Dec. 22, 2017, all of whichare incorporated by reference in their entirety herein.

BACKGROUND

The present invention relates to a functionalized ethylene and propylenecopolymer composition and a process for the manufacture of the same.

Thermoplastic elastomers (TPE), sometimes referred to as thermoplasticrubbers, are a class of copolymers or a physical mix of polymers(usually a plastic and a rubber), which consist of materials with boththermoplastic and elastomeric properties. The cross-links in TPE's canbe of physical nature, based on e.g. phase separation, crystallization,ionic or other electrostatic interactions and/or hydrogen bonding, orchemical nature, i.e. reversible covalent bonds.

Polyolefin-based TPE copolymers are typically semi-crystallinepolyolefins with varying levels of crystallinity and are typicallyclassified as POP's or POE's. Typically, these are random copolymers ofethylene and α-olefins such as propylene, 1-butene, 1-hexene or1-octene. The presence of the comonomer disturbs the crystallinity ofthe polymer and the amount of comonomer determines the softness of thematerial. A drawback of these materials is that with increasingcomonomer content—generally—also the melting point drops, which limitsthe thermal application window of the material. The upper temperature atwhich the material can be used decreases, especially since the heatdeflection temperature (HDT), which is the temperature at which apolymer deforms under a specific load, may decrease, whereas tensilecreep at a certain temperature may increase.

Functionalized polyolefins are known in the art.

For example, EP 3034545 discloses a process for the preparation of agraft copolymer comprising a polyolefin main chain and one or multiplepolymer side chains, the process comprising the steps of:

A) copolymerizing at least one first type of olefin monomer and at leastone second type of metal-pacified functionalized olefin monomer using acatalyst system to obtain a polyolefin main chain having one or multiplemetal-pacified functionalized short chain branches, the catalyst systemcomprising:

-   -   i) a metal catalyst or metal catalyst precursor comprising a        metal from Group 3-10 of the IUPAC Periodic Table of elements;    -   ii) optionally a co-catalyst;        B) reacting the polyolefin main chain having one or multiple        metal-pacified functionalized short chain branches obtained in        step A) with at least one metal substituting agent to obtain a        polyolefin main chain having one or multiple functionalized        short chain branches;        C) forming one or multiple polymer side chains on the polyolefin        main chain, wherein as initiators the functionalized short chain        branches on the polyolefin main chain obtained in step B) are        used to obtain the graft copolymer.

EP 1186619 discloses inter alia a polar group-containing olefincopolymer comprising a constituent unit represented by the followingformula (1), a constituent unit represented by the following formula (2)and a constituent unit represented by the following formula (3), havinga molecular weight distribution (Mw/Mn) of not more than 3, and havingan intensity ratio of Tαβ to Tαα+Tαβ (Tαβ/Tαα+Tαβ)), as determined froma ¹³C-NMR spectrum of said copolymer, of not more than 1.0:

wherein R¹ and R² may be the same or different and are each a hydrogenatom or a straight-chain or branched aliphatic hydrocarbon group of 1 to18 carbon atoms; R³ is a hydrocarbon group; R⁴ is a hetero atom or agroup containing a hetero atom; r is 0 or 1; X is a polar group selectedfrom an alcoholic hydroxyl group, a phenolic hydroxyl group, acarboxylic acid group, a carboxylic acid ester group, an acid anhydridegroup, an amino group, an amide group, an epoxy group and a mercaptogroup; p is an integer of 1 to 3; and when p is 2 or 3, each X may bethe same or different, and in this case, if r is 0, X may be bonded tothe same or different atom of R³, and if r is 1, X may be bonded to thesame or different atom of R⁴.

WO 97/42236 discloses a process to produce functionalized polyolefins bycopolymerizing at least one polar monomer and at least one olefin undereffective copolymerization conditions using a catalyst system containinga transition metal complex and a cocatalyst. The at least one olefin canbe the predominate monomer forming the functionalized polyolefin chain.The transition metal complex includes a transition metal having areduced valency, which is selectable from groups 4-6 of the PeriodicTable of the Elements, with a multidentate monoanionic ligand and withtwo monoanionic ligands. A polar monomer has at least one polar groupand that group is reacted with or coordinated to a protecting compoundprior to the copolymerization step.

There remains a need for a random polyethylene and propylene copolymerhaving a higher upper limit for the temperature at which it can be usedfor various applications.

SUMMARY

It is therefore an object of the present invention to provide anethylene and propylene copolymer composition in which the abovementionedand/or other problems are solved and in particular which have improvedproperties in terms of their upper temperature of use.

Without willing to be strictly bound to it the present inventors believethat the functionalities of certain functionalized polyolefins tend tocluster which in itself means that a certain degree of cross-linking isinherently present in at least some types of functionalized polyolefins.The present inventors however further found that these cross-links canbe enhanced by addition of certain materials that interact with thefunctionalities of the functionalized polyolefins. In particular, thepresent inventors found that materials capable of forming hydrogen bondscan provide advantageous properties to the functionalized polyolefins.

Accordingly, the present invention relates to a process for themanufacture of a functionalized ethylene and propylene copolymercomposition comprising the steps of:

a) copolymerizing ethylene, propylene and at least one maskedfunctionalized olefin monomer in the presence of a catalyst system,

wherein the masked functionalized olefin monomer is a reaction productof a functionalized olefin monomer represented by the structureaccording to Formula (I) and a masking agent:

wherein R², R³, and R⁴ are each independently selected from the groupconsisting of H and hydrocarbyl with 1 to 16 carbon atoms,wherein R⁵—[X—(R)_(n)]_(m) is a polar functional group containing one ormultiple heteroatom containing functionalities X—(R⁶)_(n) whereinX is selected from —O—, —S— or —CO₂— and R⁶ is H, and n is 1, orX is N and R⁶ is each independently selected from the group consistingof H and a hydrocarbyl group with 1 to 16 carbon atoms, and n is 2,wherein R⁵ is either —C(R^(7a))(R^(7b))— or a plurality of—C(R^(7a))(R^(7b))— groups, wherein R^(7a), and R^(7b) are eachindependently selected from the group consisting of H or hydrocarbylwith 1 to 16 carbon atoms and R⁵ comprises 1 to 10 carbon atoms,wherein R³ and R⁵ may together form a ring structure that isfunctionalized with one or multiple X—(R⁶)_(n),where X is attached to either the main chain or side chain of R⁵, wherem is an entire number between 1 and 10, preferably 1 or 2, andb) treating the product obtained by step a) with a Brønsted acidsolution, optionally containing metal salts or ammonium salts, capableto abstract the residue derived from the masking agent and combining theobtained functionalized ethylene and propylene copolymer with across-linking enhancing agent selected from the group consisting ofpolyols, polyamines, polyacids, polyethers, polyesters, polycarbonates,polyamides, polyurethanes, polyureas, polysaccharides, polypeptides andcombinations of at least two of said cross-linking enhancing agents,wherein said cross-linking enhancing agent has at least twofunctionalities.

DETAILED DESCRIPTION

A hydrocarbyl in the sense of the invention may be a substituentcontaining hydrogen and carbon atoms; it is a linear, branched or cyclicsaturated or unsaturated aliphatic substituent, such as alkyl, alkenyl,alkadienyl and alkynyl; alicyclic substituent, such as cycloalkyl,cycloalkadienyl cycloalkenyl; aromatic substituent, such as monocyclicor polycyclic aromatic substituent, as well as combinations thereof,such as alkyl-substituted aryls and aryl-substituted alkyls. It may besubstituted with one or more non-hydrocarbyl, heteroatom-containingsubstituents.

A functionalized olefin monomer in the sense of the invention may be anolefin monomer comprising a polar functional group, especially a proticfunctional group, such as for example an alcohol, an acid, a thiol or anamine.

According to the invention, the functionalized ethylene and propylenecopolymer of the ethylene and propylene copolymer composition may beamorphous or semi-crystalline.

The term “semi-crystalline” is known to a skilled person per se. For theavoidance of doubt and in the context of the present invention,semi-crystalline means that a melting endotherm as measured bydifferential scanning calorimetry (DSC) can be observed. Thefunctionalized ethylene and propylene copolymer is determined to besemi-crystalline by DSC when there is a melting endotherm within therange of 25° C. to 300° C. in the second heating curve at a heating rateof 10° C./min.

The term “amorphous” is known to a skilled person per se. For theavoidance of doubt and in the context of the present invention the term“amorpohous” means that no melting endotherm as measured by DSC isobserved. The functionalized ethylene and propylene copolymer isdetermined to be amorphous by DSC when there is no melting endothermwithin the range of 25° C. to 300° C. in the second heating curve at aheating rate of 10° C./min.

The copolymer prepared in step a), i.e. the functionalized ethylenepropylene copolymer is a random copolymer.

Advantageously, the functionalized ethylene and propylene copolymercomposition according to the invention may have a broad applicationwindow, especially a higher heat deflection temperature (HDT) asmeasured for example according to ASTM 648 and/or a reduced tensilecreep at a certain temperature, which may be measured according toISO899-1 compared to non-functionalized polyethylene and polypropyleneswith a similar crystallinity.

Cross-linked in the sense of the present invention may mean havinginteractions between different polymer chains. Interactions may therebybe for example hydrogen bonding interactions or electrostaticinteractions of the polar functionalities of different polymers chains,especially for example by clustering of the polymer functionalities inpolar aggregates/domains. This may lead to cross-linked systems offunctionalized ethylene and propylene copolymers. The term“cross-linking enhancing agent” thus means a material that is capable offorming one or more of the abovementioned interactions with differentpolymer chains of the functionalized polyolefin. As such “cross-links”are created and/or reinforced by the use of the said cross-linkingenhancing agents.

Functionalized ethylene and propylene copolymer compositions accordingto the invention may comprise at least one type of reversiblecross-links or at least two types of different reversible cross-links,whereby preferably for example at least one type of reversiblecross-links may be based on crystallization and/or at least one type ofreversible cross-links may be based on hydrogen bonding interactions.The cross-linking enhancing agent thereby essentially enhances orcreates the type cross-links based on hydrogen and/or electrostaticinteractions. The cross-linking enhancing agent does not affect thecross-links based on crystallization of the functionalized ethylenepropylene copolymer as such.

Cross-linked polymer systems containing at least two types of differentcross-links consisting of at least one type of reversible cross-links(often called transient) may be capable of dissipating strain energy,preferably for example leading to an improved fracture toughness, andmay be capable of storing elastic energy, preferable for example givingrise to shape-memory and self-healing properties.

Having at least two types of different reversible cross-links maythereby allow for good processability and/or recyclability at hightemperature where network interactions are weakened while still havingthe full benefit of a dual network system at lower temperatures, wherenetwork interactions may improve material properties and/or provideunique material properties.

Shape memory (co)polymers are responsive polymers that can adopt desireddeformed temporary shapes upon the simultaneous action of a mechanicaldeformation and of an external stimulus (i.e., heating above theirtransition temperature). Furthermore, shape memory (co)polymers canrecover their original shapes simply upon applying the same or adifferent external stimulus (e.g., heating above their transitiontemperature).

Shape memory (co)polymers generally contain two types of differentcross-links, whereby at least one needs to be a reversible cross-link(called transient). When these double cross-linked materials deform, thetransient bonds may break and dissipate strain energy. The presence ofthese transient bonds may also delay macroscopic rupture. Both theseeffects contribute to an increase in fracture toughness. When the samematerials are heated to break the transient cross-links, deformed andsubsequently cooled under strain to reform the transient cross-links,the formation of the transient cross-links fixes the material in thetemporary shape. Upon reheating, the transient cross-links may breakagain so that the system recovers to the initial shape.

Furthermore, reversible cross-links that can reform for example uponheating may help with self-healing properties.

According to the invention, the functionalized ethylene and propylenecopolymer composition may comprise at least one type of reversiblecross-links or at least two types of different reversible cross-linksand/or may be used as shape memory copolymers and/or self-healingcopolymers and/or may show improved fracture toughness.

Moreover, the functionalized ethylene and propylene copolymercomposition according to the invention that may comprise at least onetype of reversible cross-links or at least two types of differentreversible cross-links may be especially easy to process and/or torecycle, preferably while having good mechanical properties and/or agood mechanical stability, especially for example at lower temperatures.

According to the invention, a Brønsted acid solution capable to abstractthe residue derived from the masking agent from the functionalizedethylene and propylene copolymer may comprise for example inorganicacids such as for example hydrochloric acid, hydrobromic acid,hydroiodic acid, hydrofluoric acid, phosphoric acid, sulfuric acid,nitric acid or organic acids such as for example formic acid, aceticacid, citric acid, ethylenediaminetetraacetic acid or a partiallyneutralized carboxylic acid-containing chelates, such as EDTA salts,especially disodium edetate (a disodium salt of EDTA), or combinationsof those. The so-called “de-masking” step using a Brønsted acid is knownper se.

According to the invention, a metal salt used is step b) may be forexample a fluoride, chloride, bromide, iodide, hydroxide, nitrite,nitrate, formate, acetate, bicarbonate, carbonate, sulfite, sulfate,chlorate, perchlorate or bromate selected from the metals like Li, Na,K, Mg, Ca, Sr, Ba, Zn, Cu, Sn, Ag, Fe, Cr, Al or Ga. Preferably alkalimetal salts.

According to the invention, ammonium salts used is step b) may be forexample fluoride, chloride, bromide, iodide, hydroxide, nitrite,nitrate, formate, acetate, bicarbonate, carbonate, sulfite, sulfate,chlorate, perchlorate, bromate or EDTA salts of for example theprotonated forms of NH₃, MeNH₂, Me₂NH, EtNH₂, BuNH₂, Et₂NH, NMe₃, NEt₃,ethylene diamine, N,N,N′,N′-tetramethyl ethylene diamine,1,3-diaminopropane, hexamethylenediamine, piperazine, diethylenetriamine, N,N,N′,N″,N″-pentamethyl diethylene triamine,polyethylenimine.

It was found that the functionalized ethylene and propylene copolymercomposition according to the invention has a high heat deflectiontemperature (HDT), good ductile properties at lower temperature as wellas low tensile-creep and good elastic properties at higher temperatures,which allow it to be used for various applications. The functionalizedethylene and propylene copolymer is processable at elevatedtemperatures, indicating that either a thermal reversible or a dynamiccross-linked system may exist.

The strength of the hydrogen bonding and/or electrostatic interactionswithin the functionalized ethylene and propylene copolymer can be tunedby selecting the proper functionality and by the amount of thecross-linking enhancing agents.

According to the invention, cross-linking enhancing agents are agentsthat strengthen the inter-polymer interactions as explained above.According to the invention, such cross-linking enhancing agents arepolyols, polyamines, polyacids, polyethers, polyesters, polycarbonates,polyamides, polyurethanes, polyureas, polysaccharides, polypeptides andcombinations of at least two of said cross-linking enhancing agents. Inthat respect the term “poly” means a material having two or morefunctionalities that are capable of interacting with the functionalizedpolyolefin. Examples of such polyfunctional materials include ethyleneglycol, glycerol, pentaerythritol, mucic acid, galactaric acid,carbohydrates, ethylene diamine, diethylene triamine, tetramethylethylene diamine, pentamethyl diethylene triamine, polyethylenimine,maleic acid, succinic acid, tartaric acid, citric acid, polyacrylicacid, poly(ethylene-co-acrylic acid), polyvinyl acetate,poly(ethylene-co-vinyl acetate), polyvinyl alcohol,poly(ethylene-co-vinyl alcohol), polyethylene oxide, polypropyleneoxide, poly(ethylene oxide-co-propylene oxide), poly(ethylenecarbonate), poly(propylene carbonate), polycaprolactone, poly(ethylenebrassylate), polylactide, polybutylene adipate, polybutylene adipateterephthalate, polyamide 6, polyamide 4,6, polyamide 6,6 andcombinations of at least two of the foregoing cross-linking enhancingagents. Preferred materials are those capable of forming hydrogen bondswith the functionalized polyolefin.

The amount of cross-linking enhancing agent is preferably from 0.01 to10 wt. %, preferably from 0.03 to 7 wt. %, more preferably from 0.05 to5 wt. %, based on the combined weight of the functionalized ethylene andpropylene copolymer and the cross-linking enhancing agent.

The functionalized ethylene and propylene copolymer compositionaccording to the invention may show for example good abrasion and scuffresistance, chemical resistance, oil resistance, antistatic properties,moisture absorption properties, surface hydrophilic properties,antifungal properties.

The functionalized ethylene and propylene copolymer compositionsaccording to the invention can be used as an elastomeric or rubberymaterial. In particular, the functionalized ethylene and propylenecopolymer composition according to the invention can replace theexisting elastomeric material used in high temperature applications suchas thermoplastic polyurethane and thermoplastic vulcanisates.

The functionalized ethylene and propylene copolymers according to theinvention has a good flowability and processability.

Step a)

Polymerization

According to the invention ethylene and propylene and one or multiplefunctionalized olefin monomer(s) are polymerized.

According to the invention, the ethylene to propylene weight ratio instep a) is preferably from 20:80 to 70:30, preferably from 25:75 to60:40.

The polymerization step may use two, three or more types offunctionalized olefin monomers.

Functionalized Olefin Monomer

The functionalized olefin monomer has the following structure and is areaction product of a compound represented by the structure according toFormula (I) and a masking agent:

wherein R², R³, and R⁴ are each independently selected from the groupconsisting of H and hydrocarbyl with 1 to 16 carbon atoms,wherein R⁵—[X—(R)_(n)]_(m) is a polar functional group containing one ormultiple heteroatom containing functionalities X—(R⁶)_(n) whereinX is selected from —O—, —S— or —CO₂— and R⁶ is H, and n is 1, orX is N and R⁶ is each independently selected from the group consistingof H and a hydrocarbyl group with 1 to 16 carbon atoms, and n is 2,wherein R⁵ is either —C(R^(7a))(R^(7b))— or a plurality of—C(R^(7a))(R^(7b))— groups, wherein R^(7a), and R^(7b) are eachindependently selected from the group consisting of H or hydrocarbylwith 1 to 16 carbon atoms and R⁵ comprises 1 to 10 carbon atoms,wherein R³ and R⁵ may together form a ring structure that isfunctionalized with one or multiple X—(R⁶)_(n),where X is attached to either the main chain or side chain of R⁵, wherem is an entire number between 1 and 10, preferably 1 or 2.

Preferably, X is selected from —O— or —CO₂—.

In a preferred embodiment, the functionalized olefin monomer accordingto Formula I is a hydroxyl- or carboxylic acid-bearing α-olefin orhydroxyl- or carboxylic acid-functionalized ring-strained cyclic olefin,preferably a hydroxyl, a dihydroxyl or carboxylic acid α-olefin.

Hydroxyl-bearing functionalized olefin monomers may correspond forexample to Formula I wherein R², R³, and R⁴ are each H and wherein X is—O— and wherein R⁵ is either —C(R^(7a))(R^(7b))— or a plurality of—C(R^(7a))(R^(7b))— groups, wherein R^(7a), and R^(7b) are eachindependently selected from the group consisting of H or hydrocarbylwith 1 to 16 carbon atoms. Examples of R⁵ groups are —(CH₂)₉— and—(CH₂)₂—.

Further examples of the hydroxyl-functionalized functionalized olefinmonomer include, but are not limited to allyl alcohol, 3-buten-1-ol,3-buten-2-ol, 3-buten-1,2-diol, 5-hexene-1-ol, 5-hexene-1,2-diol,7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol and 10-undecene-1-ol.

Even further examples of functionalized olefin monomer includehydroxyl-functionalized ring-strained cyclic olefins (also calledinternal olefins), which may be for example typicallyhydroxyl-functionalized norbornenes, preferably 5-norbornene-2-methanol.They correspond to Formula I wherein R² and R⁴ are H and R³ and R⁵together for a ring structure that is functionalized with X—H, wherein Xis —O—.

Carboxylic acid-bearing functionalized olefin monomers may for examplecorrespond to Formula I wherein R², R³, and R⁴ are each H and wherein Xis —CO₂— and wherein R⁵ is either —C(R^(7a))(R^(7b))— or a plurality of—C(R^(7a))(R^(7b))— groups, wherein R^(7a), and R^(7b) are eachindependently selected from the group consisting of H or hydrocarbylwith 1 to 16 carbon atoms. An example of an R⁵ group is —(CH₂)₈—.Preferred acid functionalized olefins monomers may be selected from thegroup of 4-pentenoic acid or 10-undecenoic acid.

Accordingly, it is preferred that the functionalized monomer is selectedfrom the group consisting of allyl alcohol, 3-buten-1-ol, 3-buten-2-ol,3-buten-1,2-diol, 5-hexene-1-ol, 5-hexene-1,2-diol, 7-octen-1-ol,7-octen-1,2-diol, 9-decen-1-ol, 10-undecene-1-ol,5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid or10-undecenoic acid, preferably 3-buten-1-ol, 3-buten-2-ol,10-undecen-1-ol, 4-pentenoic acid and 10-undecenoic acid.

It is preferred that the amount of the functionalized olefin monomers instep a) is from 0.01 to 30 mol %, preferably from 0.02 to 20 mol % orfrom 0.05 to 10 mol %, with respect to the total molar amount of theolefin monomers and the functionalized olefin monomers. Most preferredis a range of 0.1 to 5 mol %.

Masking Agent

The hydrogen atoms (R⁶) directly bound to X in the functionalized olefinmonomer has a Brønsted acidic nature poisonous to the highly reactivecatalyst. A masking agent is used, which can react with the acidichydrogen and binds to the monomer comprising the polar group. Thisreaction will prevent a reaction of the acidic polar group (—X—H) withthe catalyst and will hamper coordination of the polar group (—X—) tothe catalyst.

The molar amount of the masking agent preferably is at least the samemolar amount as monomer of formula (I) used in the process according tothe invention. Preferably, the molar amount of masking agent is at least10 mol % higher than the amount of monomer of formula (I), or at last 20mol % higher. Typically, the amount of masking agent is less than 500mol % of monomer according to formula (I). In some occasions higheramounts may be used or may be necessary.

Examples of masking agents are silyl halides, trialkyl aluminumcomplexes, dialkyl magnesium complexes, dialkyl zinc complexes ortrialkyl boron complexes. In the process of the invention it ispreferred that the masking agent is selected from trialkyl aluminumcomplexes, dialkyl magnesium complexes, dialkyl zinc complexes ortrialkyl boron complexes. Preferred complexes are trialkyl aluminumcomplexes. Preferably, these trialkyl aluminum complexes have bulkysubstituents, like for example isobutyl groups. The most preferredmasking agent is triisobutylaluminum.

Metal Catalyst and/or Catalyst Precursor Suitable for the ProcessAccording to the Invention.

The process according to the invention is performed in the presence of asuitable catalyst system.

In the section below several examples for single-site catalystprecursors, which may be used to prepare the metal catalyst used in thepresent invention, are specified. Metal catalysts that are suitable maybe obtained by reacting the metal catalyst precursors with a co-catalysteither prior to the use in the polymerization or by in situ reactionwith a co-catalyst.

A single-site-catalyst is a catalyst that contains a single,catalytically active, metal center. The metal atom has an opencoordination site where it binds olefins, which are subsequentlypolymerized. Single-site catalysts precursors include those found inChem. Rev. 2000, 100, 1167-1682. A special case of single-site catalystsforms the multinuclear catalysts consisting of different butwell-defined (single-site) catalytic sites within one and the samecatalyst molecule. Examples of such multinuclear catalysts can be foundin Chem. Rev. 2011, 111, 2450-2485.

Examples of single-site catalysts are metallocene catalysts. Typically,a metallocene catalyst refers to a sandwich complex comprising atransition metal, group 3 metal or lanthanide coordinated to two membersof five-member carbon ring, i.e. substituted cyclopentadienyl (Cp),hetero-substituted five- or six-membered aromatic ring, or a bridged(ansa) ligand consisting of five-member carbon rings and/orhetero-substituted five- or six-membered aromatic rings.

Other examples of single-site catalysts are half-metallocenes.Half-metallocene catalysts in the present description may meanespecially for example: a metal catalyst or catalyst precursor typicallyconsisting of one five-member carbon ring, i.e. substitutedcyclopentadienyl (Cp), hetero-substituted five- or six membered aromaticring bound to a metal active site.

Other examples of single-site catalysts are post-metallocenes.Post-metallocene catalysts in the present description may meanespecially for example: a metal catalyst that contains no substitutedcyclopentadienyl (Cp) ligands, but may contains one or more anions boundto the metal active site, typically via a heteroatom.

Examples of half-metallocene and post-metallocene catalyst precursorscan for example be found in Chem. Rev. 2003, 103, 283-315, Chem. Rev.2011, 111, 2363-2449 and Angew. Chem. Int. Ed. 2014, 53, 9722-9744.Examples of late transition metal catalysts can for example be found in:Chem. Rev. 2015, 115, pp 12091-12137

Examples of supported single-site catalyst systems can for example befound in Chem. Rev. 2005, 105, 4073-4147.

In the single-site catalyst or single-site catalyst precursors, whichmay be used in the invention, the transition metal might not be presentin its highest oxidation state, but in a lower oxidation state. The“oxidation state” of an atom in a molecule gives the number of valenceelectrons it has gained or lost. The highest oxidation state of titaniumis +4 and of chromium is +6. These metals can be present in the catalystused in the process according to the present invention in a loweroxidation state: titanium preferably as Ti³⁺, chromium as Cr³⁺. This maycontribute to reduce the catalyst's sensitivity to poisoning bynucleophilic functions of the comonomer.

Suitable metal catalyst precursors can be also the trivalent transitionmetal as those described in WO 9319104 or in WO 9613529.

According to the invention, said low valent catalyst precursor can befor example [(C₅H₄)CH₂CH₂N(Me)₂]MCl₂, [(C₅Me₄)CH₂CH₂N(Me)₂]MCl₂,[(C₅H₄)CH₂CH₂N(i-Pr)₂]MCl₂, [(C₅Me₄)CH₂CH₂N(i-Pr)₂]MCl₂,[(C₅H₄)CH₂CH₂N(n-Bu)₂]MCl₂, [(C₅Me₄)CH₂CH₂N(n-Bu)₂]MCl₂,[(C₉H₆)CH₂CH₂N(Me)₂]MCl₂, [(C₉H₆)CH₂CH₂N(i-Pr)₂]MCl₂,[(C₅Me₄)C₉H₆N]MCl₂, [(C₅Me₃(SiMe₃))C₉H₆N]MCl₂, [(C₉H₆)C₉H₆N]MCl₂,[(C₅Me₄)CH₂C₅H₄N]MCl₂ or [(C₉H₆)CH₂C₅H₄N]MCl₂, where M is titanium orchromium.

Other non-limiting examples of metal catalyst precursors that would besuitable according to the present invention are:(pyrrolidinyl)ethyl-tetramethylcyclopentadienyl titanium dichloride,(N,N-dimethylamino)ethyl-fluorenyl titanium dichloride,(bis(1-methyl-ethyl)phosphino)ethyl-tetramethylcyclopentadienyl titaniumdichloride,(bis(2-methyl-propyl)phosphino)ethyl-tetramethylcyclopentadienyltitanium dichloride,(diphenylphosphino)ethyl-tetramethylcyclopentadienyl titaniumdichloride,(diphenylphosphino)methyldimethylsilyl-tetramethylcyclopentadienyltitanium dichloride.

In a preferred embodiment of the invention, the metal catalyst precursoris [(C₅Me₄)CH₂CH₂N(Me)₂]TiCl₂.

According to the invention, other suitable low valent catalystprecursors can be for example{N′,N″-bis[2,6-di(1-methylethyl)phenyl]-N,N-diethylguanidinato} metaldichloride,{N′,N″bis[2,6-di(1-methylethyl)phenyl]-N-methyl-N-cyclohexylguanidinato}metal dichloride,{N′,N″-bis[2,6-di(1-methylethyl)phenyl]-N,N-pentamethyleneguanidinato}metal dichloride,{N′,N″-bis[2,6-di(methyl)phenyl]-sec-butyl-aminidinato} metaldichloride, {N,N′-bis(trimethylsilyl)benzamidinato} metal dichloride,{N-trimethylsilyl,N′—(N″,N″-dimethylaminomethyl)benzamidinato} metaldichloride and their THF or other Lewis base adducts, where metal istitanium or chromium.

In a preferred embodiment of the invention, the metal catalystprecursors are [C₆H₅C(NSiMe₃)₂]TiCl₂(THF)₂ and[C₆H₅C(NSiMe₃)CH₂CH₂N(CH₃)₂]TiCl₂(THF).

Other examples of suitable catalysts are so-called metallocene catalystsprecursors, including zirconocene and hafnocene dichloride metalcatalyst precursors, as for example described in WO2016102690, WO9411406, U.S. Pat. No. 6,342,622 and WO 2017118617.

In another embodiment, the metal catalysts or metal catalyst precursorsis bis(n-butyl-cyclopentadienyl) zirconium dichloride,bis(pentamethylcyclopentadienyl) zirconium dichloride,bis(2-phenyl-indenyl) zirconium dichloride,rac-dimethylsilyl-bis(1-indenyl) zirconium dichloride,rac-dimethylsilyl-bis(2-methyl-1-indenyl) zirconium dichloride,rac-dimethylsilyl-bis(2-methyl-4-phenyl-1-indenyl) zirconium dichloride,diphenylmethylene-(cyclopentadienyl)(2,7-di-t-butyl-fluorenyl) zirconiumdichloride,diphenylmethylene-(3-methyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride,diphenylmethylene-(3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride,diphenylmethylene-(cyclopentadienyl)(2,7-di-t-butyl-fluorenyl) hafniumdichloride,diphenylmethylene-(3-methyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)hafnium dichloride,diphenylmethylene-(3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)hafnium dichloride, rac-methylene-bis(3-t-butyl-1-indenyl) zirconiumdichloride, rac-dimethylmethylene-bis(3-t-butyl-1-indenyl) zirconiumdichloride, rac-methylene-bis(3-t-butyl-1-indenyl) hafnium dichloride,rac-dimethylmethylene-bis(3-t-butyl-1-indenyl) hafnium dichloride,rac-dimethylsilyl-bis(1-indenyl) hafnium dichloride,dimethylsilyl(1,3-dimethyl-inden-2-yl)(2,4-diphenyl-inden-1-yl) hafniumdimethyl,dimethylsilyl(2-phenyl-inden-1-yl)(2,3,4,5-tetramethylcyclopentyl)hafnium dimethyl, dimethylsilyl(1,3-dimethyl-inden-2-yl)(2-phenyl-inden-1-yl) hafnium dimethyl,[2,2′-di-(cyclopenta[a]naphthalen-2-yl)biphenyl]zirconium dichloride,[2,2′-bis(cyclopenta[a]naphthalene-2-yl)biphenyl]hafnium dichloride,[2,2′-bis(cyclopenta[al naphthalene-2-yl)-4,4′-di-tert-butylbiphenyl]zirconium dichloride,[2,2′-bis(cyclopenta[a]naphthalene-2-yl)-4,4′-di-tert-butylbiphenyl]zirconiumdichloride,[2,2′-bis(cyclopenta[a]naphthalene-2-yl)-4,4′,5,5′-tetramethylbiphenyl]zirconiumdichloride,[2,2′-bis(cyclopenta[a]naphthalene-2-yl)-4,4′,5,5′-tetramethylbiphenyl]zirconiumdichloride,[2,2′-Bis(5-6,7,8,9-tetrahydro-cyclopenta[a]naphthalene-2-yl)-4,4′-di-tertbutyl-biphenyl]zirconiumdichloride, rac-diethylsilyl-bis(5-cyclopenta[a]naphthalen-2-yl)zirconium dimethyl,dimethylsilyl(1,3-dimethyl-inden-2-yl)(2,4-diphenyl-inden-1-yl)zirconium dichloride, dimethylsilyl(2-phenyl-inden-1-yl)(2,3,4,5-tetramethylcyclopentyl) zirconiumdichloride, dimethylsilyl(1,3-dimethyl-inden-2-yl) (2-phenyl-inden-1-yl)zirconium dichloride, dimethylsilyl (1,3-dimethyl-inden-2-yl)(2-phenyl-cyclopenta[a]naphthalen-3-yl) zirconium dichloride,dimethylsilyl (1,3-dimethyl-inden-2-yl)(2-phenyl-cyclopenta[a]naphthalen-3-yl) hafnium dimethyl.

In another embodiment, the metal catalysts or metal catalyst precursorsare rac-dimethylsilyl bis(2-methyl-4-phenyl-1-indenyl) zirconiumdichloride, dimethylsilylbis(1,3-dimethyl-inden-2-yl)(2,4-diphenyl-inden-1-yl) hafnium dimethyl,dimethylsilyl(1,3-dimethyl-inden-2-yl)(2-phenyl-cyclopenta[a]naphthalen-3-yl)zirconium dichloride.

According to the invention, examples of suitable catalysts are so-calledconstrained geometry catalysts. Non-limiting examples of titanium(IV)dichloride metal catalyst precursors according to Formula XIV suitablefor use in the present invention are:(N-t-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane titaniumdichloride, (N-phenylamido)(dimethyl)(tetramethylcyclopentadienyl)silane titanium dichloride,(N-sec-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane titaniumdichloride, (N-sec-dodecylamido)(dimethyl)(fluorenyl)silane titaniumdichloride, (3-phenylcyclopentadien-1-yl) dimethyl(t-butylamido) silanetitanium dichloride, (3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silane titanium dichloride,(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido) silane titaniumdichloride, 3-(3-N,N-dimethylamino)phenyl)cyclopentadien-1-yl)dimethyl(t-butylamido) silane titanium dichloride,(P-t-butylphospho)(dimethyl) (tetramethylcyclopentadienyl) silanetitanium dichloride.

In another embodiment of the metal catalyst precursor is(N-t-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane titaniumdichloride.

The metal catalysts or metal catalyst precursors for use in the presentinvention may also be from the group of metal catalysts or metalcatalyst precursors having no cyclopentadienyl groups, in other words,non-cyclopentadienyl metal catalysts or metal catalyst precursors.

In a preferred embodiment of the metal catalyst precursor is[N-(2,6-di(I-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl orbis[2-(1,1-dimethylethyl)-6-[(pentafluorophenylimino)methyl]phenolato]titaniumdichloride.

Co-Catalysts

A co-catalyst can be used when a metal catalyst precursor is applied.The function of this co-catalyst is to activate the metal catalystprecursor. Co-catalysts may be selected for example from the groupconsisting of aluminum alkyls and aluminum alkyl halides, such as forexample triethyl aluminum (TEA) or diethyl aluminum chloride (DEAC),MAO, DMAO, MMAO, SMAO, solid MAO, possibly in combination with aluminumalkyls, for example triisobutyl aluminum, and/or with a combination ofan aluminum alkyl, for example triisobutyl aluminum, and a fluorinatedaryl borane or fluorinated aryl borate (viz. B(R′)_(y) wherein R′ is afluorinated aryl and y is 3 or 4, respectively). Examples of afluorinated borane is B(C₆F₅)₃ and of fluorinated borates are[X]⁺[B(C₆F₅)₄]⁻ (e.g. X=Ph₃C, C₆H₅N(H)Me₂). For more examples see forexample Chem. Rev. 2000, 100, 1391-1434.

For example, the co-catalyst can be an organometallic compound. Themetal of the organometallic compound can be selected from Group 1, 2, 12or 13 of the IUPAC Periodic Table of Elements. Preferably, theco-catalyst is an organoaluminum compound, more preferably analuminoxane, said aluminoxane being generated by the reaction of atrialkyl aluminum compound with water to partially hydrolyze saidaluminoxane. For example, trimethyl aluminum can react with water(partial hydrolysis) to form methylaluminoxane (MAO). MAO has thegeneral formula (Al(CH₃)_(3-n)O_(0.5))_(x)—(AlMe₃)_(y) having analuminum oxide framework with methyl groups on the aluminum atoms.

MAO generally contains significant quantities of free trimethyl aluminum(TMA), which can be removed by drying the MAO to afford the so-calleddepleted MAO or DMAO.

Alternatively to drying the MAO, when it is desired to remove the freetrimethyl aluminum, a bulky phenol such as butylhydroxytoluene (BHT,2,6-di-t-butyl-4-methylphenol) can be added which reacts with the freetrimethyl aluminum.

Supported MAO (SMAO) may also be used and may be generated by thetreatment of an inorganic support material, typically silica, by MAO.Solid MAO may also be used and may be generated as described inUS2013/0059990 and WO 2017090585 A1.

Other examples of polymeric or oligomeric aluminoxanes are tri(isobutyl)aluminum- or tri(n-octyl) aluminum-modified methylaluminoxane, generallyreferred to as modified methylaluminoxane, or MMAO.

Neutral Lewis acid modified polymeric or oligomeric aluminoxanes mayalso be used, such as alkylaluminoxanes modified by addition of ahydrocarbyl substituted Group 13 compound having 1 to 30 carbons,especially a tri(hydrocarbyl) aluminum- or tri(hydrocarbyl) boroncompounds, or a halogenated (including perhalogenated) derivativesthereof, having 1 to 10 carbons in each hydrocarbyl or halogenatedhydrocarbyl group, more especially a trialkyl aluminum compound.

In the present invention, MAO, DMAO, SMAO, solid MAO and MMAO may all beused as co-catalyst.

In addition, for certain embodiments, the metal catalyst precursors mayalso be rendered catalytically active by a combination of an alkylatingagent and a cation forming agent which together form the co-catalyst, oronly a cation forming agent in the case the catalyst precursor isalready alkylated, as exemplified in T. J. Marks et al., Chem. Rev.2000, 100, 1391. Suitable alkylating agents are trialkyl aluminumcompounds, preferably triisobutylalmunium (TIBA). Suitable cationforming agents for use herein include (i) neutral Lewis acids, such asC1-30 hydrocarbyl substituted Group 13 compounds, preferablytri(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more preferablyperfluorinated tri(aryl)boron compounds, and most preferablytris(pentafluorophenyl) borane, (ii) non polymeric, compatible,non-coordinating, ion forming compounds of the type [C]⁺[A]⁻ where “C”is a cationic group such as ammonium, phosphonium, oxonium, silylium orsulfonium groups and [A]⁻ is an anion, especially for example a borate.

Non-limiting examples of the anionic [“A” ] are borate compounds such asC1-30 hydrocarbyl substituted borate compounds, preferablytetra(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more preferablyperfluorinated tetra(aryl)boron compounds, and most preferablytetrakis(pentafluorophenyl) borate.

A supported catalyst may also be used, for example using SMAO as theco-catalyst. The support material can be an inorganic material. Suitablesupports include solid and particulated high surface area, metal oxides,metalloid oxides, or mixtures thereof. Examples include: talc, silica,alumina, magnesia, titania, zirconia, tin oxide, aluminosilicates,borosilicates, clays, and mixtures thereof.

Preparation of a supported catalyst can be carried out using methodsknown in the art, for example i) a metal catalyst precursor can bereacted with supported MAO to produce a supported catalyst; ii) MAO canbe reacted with a metal catalyst precursor and the resultant mixture canbe added to silica to form the supported catalyst; iii) a metal catalystprecursor immobilized on a support can be reacted with soluble MAO.

Alternatively, solid MAO can be used as cocatalyst creating a supportedcatalyst.

Scavengers

A scavenger can optionally be added in the catalyst system in order toreact with impurities that are present in the polymerization reactor,and/or in the solvent and/or monomer feed. This scavenger preventspoisoning of the catalyst during the olefin polymerization process. Thescavenger can be the same as the co-catalyst but can also independentlybe selected from the group consisting of aluminum hydrocarbyls (e.g.triisobutyl aluminum, trioctyl aluminum, trimethyl aluminum, MAO, MMAO,SMAO), zinc hydrocarbyls (e.g. diethyl zinc) or magnesium hydrocarbyls(e.g. dibutyl magnesium).

Some masking agents may also function as scavengers and some scavengersmay also function as masking agents.

The process according to the invention is best performed in a solutionprocess using a soluble homogeneous- or insoluble heterogeneous catalystsystem as described above.

In the process, the polymerization conditions, like for exampletemperature, time, pressure, monomer concentration can be chosen withinwide limits. The polymerization temperature is in the range from −10 to250° C., preferably 0 to 220° C., more preferably 25 to 200° C. Thepolymerization time is in the range of from 10 seconds to 20 hours,preferably from 1 minute to 10 hours, more preferably from 5 minutes to5 hours. The molecular weight of the polymer can be controlled by use ofhydrogen or other chain transfer agents like silanes, boranes, zincalkyls or excess aluminum alkyl species in the polymerization process.The polymerization may be conducted by a batch process, asemi-continuous process or a continuous process and may also beconducted in two or more steps of different polymerization conditions.The polyolefin produced is separated from the polymerization solvent anddried by methods known to a person skilled in the art.

In an embodiment, a hindered phenol, such as for examplebutylhydroxytoluene (BHT), may be added during the polymerizationprocess, especially for example in an amount between 0.1 and 5 mol.equivalents of main group metal compound(s), used as scavenger,cocatalyst and/or masking agent. This may contribute to increasemolecular weight and/or comonomer incorporation.

Preferably, the amount of the functionalized olefin monomers in step a)0.01 to 30 mol %, more preferably 0.02 to 20 mol % or 0.10 to 10 mol %,with respect to the total of the olefins and the functionalized olefinmonomers.

The invention may involve a further addition of other additives such asa processing stabilizer (primary antioxidant) such as Irganox 1010.

Product

In an aspect, the present invention relates to a functionalized ethyleneand propylene copolymer composition obtainable by the process disclosedherein.

The present invention also relates to a functionalized ethylene andpropylene copolymer composition comprising

i) from 90-99.99 wt. %, preferably from 93-99.97 wt. %, more preferablyfrom 95-99.95 wt. % of a functionalized ethylene and propylene copolymerof ethylene, propylene and at least one functionalized olefin monomerselected from the group consisting of allyl alcohol, 3-buten-1-ol,3-buten-2-ol, 3-buten-1,2-diol, 5-hexene-1-ol, 5-hexene-1,2-diol,7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol, 10-undecene-1-ol,5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid or10-undecenoic acid, preferably 3-buten-1-ol, 3-buten-2-ol,10-undecen-1-ol, 4-pentenoic acid and 10-undecenoic acid,ii) from 0.01 to 10 wt. %, preferably from 0.03-7 wt. %, more preferablyfrom 0.05-5 wt. % of at least one cross-linking enhancing agent selectedfrom the group consisting of polyols, polyamines, polyacids, polyethers,polyesters, polycarbonates, polyamides, polyurethanes, polyureas,polysaccharides, polypeptides, wherein said cross-linking enhancingagent has at least two functionalities,wherein the wt. % is based on the combined weight of the functionalizedethylene and propylene copolymer and the cross-linking enhancing agent.

In the ethylene propylene composition of the invention the weight ratioof ethylene to propylene in the functionalized ethylene and propylenecopolymer is preferably from 20:80 to 70:30, preferably from 25:75 to60:40.

It is preferred that the composition of the invention has a meltingenthalpy between 5 J/g and 150 J/g, preferably between 10 J/g and 120J/g, further preferred between 12 J/g and 100 J/g, further preferredbetween 13 J/g and 90 J/g, further preferred between 14 J/g and 80 J/g,further preferred between 15 J/g and 65 J/g as measured by DSC.

In an embodiment, the present invention also relates to a thermoplasticcomposition comprising the functionalized ethylene and propylenecopolymer composition of the invention disclosed herein. Such athermoplastic composition further comprises at least one thermoplasticpolymer is selected from the group consisting of polyolefins such asrandom polypropylene, polypropylene homopolymer, heterophasicpolypropylene copolymers, high density polyethylene, low densitypolyethylene, linear low density polyethylene, ethylene-propylenecopolymers, polyesters, polycarbonates, polyester-carbonates,polyurethanes, polyethers, polyetherimides, polyamides, polystyrene,polyphenylene-oxide, polyacrylates, olefin-acrylate copolymers,polysulfones.

Such a thermoplastic composition may also further comprise at least oneinorganic or organic filler material selected from the group consistingof metal oxides and such as titanium oxide, zirconium oxide, aluminumoxide, zinc oxide, iron oxide, metal carbonates such as calciumcarbonate, metal sulfates such as calcium sulfate, silicates such asmontmorillonite, smectite, talcum, mica, aluminum silicate, silica,glass, carbon-based filler such as carbon black, graphite, graphene,carbon nanotubes.

For the avoidance of doubt, it is to be understood that in thethermoplastic composition the functionalized ethylene propylenecopolymer preferably forms a minor portion of the thermoplasticcomposition. Thus, the amount of functionalized ethylene propylenecopolymer composition is preferably at most 30, preferably at most 15wt. % on the basis of the weight of the thermoplastic composition.

As explained herein the functionalized ethylene propylene copolymercomposition may be used as shape memory copolymer and/or self-healingcopolymer.

The invention also concerns a functionalized ethylene and propylenecopolymer, wherein the content of functionalized olefin monomer isbetween 0.01 and 30 mol %, preferably between 0.02 to 20 mol % or 0.05to 10 mol %, more preferably 0.1 to 5 mol %, with respect to the totalof the olefins and the functionalized olefin monomers in the copolymer.This copolymer may be manufactured using the process of the inventionexcept for the step of combining with the cross-linking enhancing agentin step b).

A functionalized ethylene and propylene copolymer according to theinvention, may thereby be so that the functionalized olefin monomer isselected from the group consisting of allyl alcohol, 3-buten-1-ol,3-buten-2-ol, 3-buten-1,2-diol, 5-hexene-1-ol, 5-hexene-1,2-diol,7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol, 10-undecene-1-ol,5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid or10-undecenoic acid, preferably 3-buten-1-ol, 3-buten-2-ol,10-undecen-1-ol, 4-pentenoic acid and 10-undecenoic acid.

The functionalized ethylene and propylene copolymer according may be sothat the functionalized ethylene and propylene copolymer comprises atleast one or two types of (different) reversible cross-links and/or thatthe functionalized ethylene and propylene copolymer can be used as shapememory copolymer and/or self-healing copolymer.

The functionalized ethylene and propylene copolymer according to theinvention, may be so that the amount of propylene in the functionalizedethylene and propylene copolymer is preferably at least 30 wt %,preferably >35 wt %, further preferred >40 wt %, further preferred >45wt % with respect to the total of the olefins and the functionalizedolefin monomers in the copolymer and/or so that amount of ethylene isbetween 20 and 70 wt. %, preferably between 25 and 60 wt. % with respectto the total of the olefins and the functionalized olefin monomers inthe copolymer.

The functionalized ethylene and propylene copolymer according to theinvention, may be so that the melting enthalpy is preferably between 5J/g and 150 J/g, preferably between 10 J/g and 120 J/g, furtherpreferred between 12 J/g and 100 J/g, further preferred between 13 J/gand 90 J/g, further preferred between 14 J/g and 80 J/g, furtherpreferred between 15 J/g and 65 J/g as measured by DSC (by the methodand with the equipment described below in the examples).

For the avoidance of doubt, it is to be understood that the copolymerprepared in step a) of the process of the invention or the copolymer inthe claimed composition is a random copolymer.

It is noted that the invention relates to all possible combinations offeatures described herein, preferred in particular are thosecombinations of features that are present in the claims It is inparticular noted that the preferred materials or preferred amounts ofmaterials as disclosed in the context of the process according to theinvention equally apply to the functionalized ethylene and propylenecopolymer and/or the functionalized ethylene and propylene copolymercomposition.

It is further noted that the term ‘comprising’ does not exclude thepresence of other elements. However, it is also to be understood that adescription on a product/composition comprising certain components alsodiscloses a product/composition consisting of these components. Theproduct/composition consisting of these components may be advantageousin that it offers a simpler, more economical process for the preparationof the product/composition. Similarly, it is also to be understood thata description on a process comprising certain steps also discloses aprocess consisting of these steps. The process consisting of these stepsmay be advantageous in that it offers a simpler, more economicalprocess.

When values are mentioned for a lower limit and an upper limit for aparameter, ranges made by the combinations of the values of the lowerlimit and the values of the upper limit are also understood to bedisclosed.

The invention is now elucidated by way of the following non-limitingexamples.

EXAMPLES

¹H and ¹³C NMR Characterization

The ethylene content and percentage of functionalization was determinedby ¹³C and ¹H NMR analysis carried out at 125° C. The samples weredissolved at 130° C. in deuterated tetrachloroethane (TCE-D2) containingbutylated hydroxytoluene (BHT) as stabilizer. The spectra were recordedin 5 mm tubes on a BrukerAvance 500 spectrometer equipped with acryogenically cooled probe head operating at 125° C.

Chemical shifts are reported in ppm versus tetramethylsilane and weredetermined by reference to the residual solvent protons.

High Temperature Size Exclusion Chromatography (HT-SEC)

The molecular weights, reported in kg-mol-1, and the PDI were determinedby means of high temperature size exclusion chromatography, which wasperformed at 150° C. in a GPC-IR instrument equipped with an IR4detector and a carbonyl sensor (PolymerChar, Valencia, Spain). Columnset: three Polymer Laboratories 13 μm PLgel Olexis, 300×7.5 mm.1,2-Dichlorobenzene (o-DCB) was used as eluent at a flow rate of 1mL·min⁻¹. The molecular weights and the corresponding PDIs werecalculated from HT SEC analysis with respect to narrow polystyrenestandards (PSS, Mainz, Germany).

Differential Scanning Calorimetry (DSC)

Thermal analysis was carried out on a DSC Q100 from TA Instruments at aheating rate of 5° C.·min⁻¹. First and second runs were recorded afterheating up to 210° C. and cooling down to ca. −40° C. at a rate of 10°C.·min. All copolymers were found to be semi-crystalline as determinedby DSC. The melting enthalpy was calculated as the area under the peakfrom the melting transition in DSC.

Example 1

The copolymerization reaction of propylene, ethylene, and TiBA-pacified10-undecenoic acid (entry 5, Table 1) was carried out in a stainlesssteel autoclave (2.2 L). The mechanical stirrer of the reactor wasoperated at 900 rpm. The reactor was first flushed with a mixture ofethylene and propylene at set flows for about 30 minutes. Pentamethylheptane diluent (300 mL), solutions of TiBA (1.0 M solution in toluene,4.0 mmol), TiBA-pacified 10-undecenoic acid (TiBA:10-undecenoicacid=2:1, 1.0 M, 10 mmol) and MAO (30 wt % solution in toluene, 3.5mmol) were added. Pentamethyl heptane was added to bring the totalvolume to 1 L. The reactor was then heated to 80° C. and the overallpressure was brought to 9 bar with a propylene/ethylene mixture (feedrate ratio 70/30) and kept at this pressure using a set ethylene andpropylene flow and a bleeding valve set at 9 bar. A solution ofrac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ catalyst precursor, prepared in aglovebox by dissolving 2 mg of solid precatalyst in 5 mL toluene (˜3.2μmol), was injected into the reactor applying an over pressure ofnitrogen. The reactor temperature was kept at 80±3° C. by cooling withan oil LAUDA system.

At the end of the reaction, the mixture was collected via a bottom drainvalve in a beaker. A mixture of acidified methanol (2.5% v/v HCl, 500mL) and Irganox 1010 (1.0 M, 1.0 mL) was added and the resultingsuspension was filtered. To remove residual aluminum, the crude productwas dispersed in toluene (300 mL) containing hydrochloric acid (5 M, 2.5v. %) and heated until a clear solution was obtained. The resultingmixture was cooled down and precipitated in an excess iPrOH. Theobtained solid was washed with a solution containing a water/isopropanolmixture (50 wt. %, 500 mL) and Irganox 1010 (1.0 M, 1.0 mmol) and theresulting suspension was filtered and dried at 60° C. in vacuo overnight(yield 46.3 g). The resulting product was analyzed by HT-SEC todetermine the molecular weight and molecular weight distribution (D),DSC to determine the crystallinity, ¹H and ¹³C NMR to determine thepercentage of functionalization and ethylene content.

Example 2

The copolymerization reaction of propylene, ethylene and TiBA-pacified10-undecen-1-ol (entry 4, Table 2) was carried out in a stainless steelBüchi reactor (0.3 L). Toluene solutions of the catalyst precursorrac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ (0.4 μmol) and of TiBA-pacified10-undecen-1-ol comonomer (TiBA:10-undecen-1-ol=1:1; 1.0 M, 10 mmol)were prepared in a glovebox. Pentamethyl heptane (120 mL), and MAO (30wt. % solution in toluene, 0.4 mmol) were injected into the reactorunder a nitrogen atmosphere. The solution was then saturated with apropylene/ethylene mixture (feet rate ratio 70/30) and stirred for 10minutes followed by the addition of TiBA-pacified 10-undecen-1-ol (1.0M, 10 mmol) and catalyst precursor solution (0.4 μmol). Then the reactorwas pressurized to the desired set point (6 bar) and the pressure wasmaintained constant for 20 min using a constant ethylene/propylene flowand a bleeding valve set at 6 bar. The reaction was stopped bydepressurizing the reactor followed by quenching by pouring the mixtureinto a beaker containing a mixture of acidified methanol (2.5 v. % HCl,300 mL) and Irganox 1010 (1.0 M, 0.5 mL). To remove residual aluminum,the crude product was dispersed in toluene (300 mL) containinghydrochloric acid (5M, 2.5 v. %) and heated until a clear solution wasobtained. The resulting mixture was cooled down and precipitated in anexcess iPrOH. The obtained solid was washed with a solution containing awater/isopropanol mixture (50 wt. %, 2×250 mL) and Irganox 1010 (1.0 M,0.5 mmol) and the resulting suspension was filtered and dried at 60° C.in vacuo overnight (yield 3.7 g). The resulting product was analyzed byHT-SEC to determine the molecular weight and molecular weightdistribution (D), DSC to determine the crystallinity, ¹H and ¹³C NMR todetermine the percentage of functionalization and ethylene content.

Example 3

The copolymerization product of example 1 (5 g; Table 1, entry 5) wasdispersed in toluene (250 mL) and heated until a clear solution wasobtained. Then poly(ethylene glycol) dimethyl ether (0.5 g; Mn=250g/mol) was added and the mixture was stirred for 15 minutes. Then thesolvent was distilled off and all volatiles were removed in vacuo andthe thus obtained material was washed with demineralised water (2×20 mL)leaving the final product as a rubbery material. The product wasanalysed by HT-SEC, DSC and ¹H NMR.

Example 4

The copolymerization product of example 2 (2.5 g; Table 2, entry 4) wasdispersed in toluene (200 mL) and heated until a clear solution wasobtained. Then a solution of branched polyethyleneimine (0.2 g;Mn=10,000 g/mol, Sigma-Aldrich) was added and the mixture was stirredfor 15 minutes. Then the solvent was distilled off and all volatileswere removed in vacuo leaving the final product as a rubbery material.The product was analyzed by HT-SEC, DSC and ¹H NMR.

Example 5

A sample of a copolymerization product obtained as described in example2 (3 g; Table 2, entry 3) was dispersed in toluene (200 mL) and heateduntil a clear solution was obtained. Then glycerol (0.6 g) was added.Then the solvent was distilled off and all volatiles were removed invacuo leaving the final product as a rubbery material. The product wasanalysed by HT-SEC, DSC and ¹H NMR.

Example 6

The copolymerization reaction of propylene with 10-undecen-1-ol wasperformed in the same way as described in example 2. At the end of thereaction, the mixture was collected via a bottom drain valve in a beakercontaining an acidified glycerol solution (2.5% v/v HCl, 100 mL) andIrganox 1010 (1.0 M, 0.5 mmol). The resulting mixture was stirred for 2h, filtered and washed with demineralised water (4×200 mL) and dried at60° C. in vacuo overnight. The product was analysed by HT-SEC, DSC and¹H NMR.

TABLE 1 Copolymerizations of ethylene, propylene and 10-undecenoic acidusing rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂/MAO catalyst. ^(a) TiBA:10-undecenoic C₂ ⁼/C₃ ⁼ Com. M_(n) acid ^(b) feed ratio Yield ^(c) incorp.(kg · Entry # (mmol) (%) (g) (mol. %) mol⁻¹) Ð 1 — 20:80 65.2 n.a 44.32.6 2 10 20:80 59.6 0.9 46.2 2.3 3 20 20:80 54.2 1.2 50.5 3.2 4 — 30:7062.4 n.a 33.1 3.4 5 10 30:70 46.3 0.6 32.3 2.6 6 20 30:70 35.7 0.8 46.52.4 ^(a) Conditions: rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ catalyst precursor(3.2 μmol), TiBA (1.0M solution in toluene) 4 mL, MAO (30 wt % solutionin toluene) = 3.5 mmol, C₃ ⁼/C₂ ⁼ feed = 9 bar, TiBA-pacified10-undecenoic acid comonomer solution (TIBA:10-undecenoic acid = 2:1),pentamethyl heptane diluent 1 L, reaction temperature 80° C., reactiontime 20 min. ^(b) Comonomer 10-undecenoic acid (1.0M solution intoluene), TiBA:10-undecenoic acid 2:1. ^(c) The yield was obtained undernon-optimised conditions. The ICP-MS revealed Al content ≤ 0.1 wt. %.

TABLE 2 Copolymerization of ethylene, propylene and 10-undecenol usingrac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂/MAO catalyst. ^(a) TiBA:10- C₂ ⁼/C₃ ⁼Com. M_(n) undecenol ^(b) feed ratio Yield incorp. (kg · Entry # (mmol)(%) (g) ^(b) (mol. %) mol⁻¹) Ð 1 — 20:80 5.4 n.a. 44.3 2.6 2 10 20:804.6 0.9 36.2 2.8 3 15 20:80 4.3 1.1 29.8 2.4 4 10 30:70 3.7 1.0 55.1 3.15 15 30:70 4.1 1.2 65.0 2.8 ^(a) Conditions:rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ catalyst precursor (0.4 μmol), MAO (30wt. % solution in toluene) Al/Zr ~1000, C₃ ⁼/C₂ ⁼ feed = 6 bar,TiBA-pacified 10-undecen-1-ol comonomer solution (TIBA:10-undecen-1-ol =1:1), pentamethyl heptane 120 mL, reaction temperature 40° C., reactiontime 20 min. ^(b) The yield was obtained under non-optimised conditionsand was determined using the weight of polymer obtained after filtrationand drying in vacuum oven overnight at 60° C. The ICP-MS revealed Alcontent ≤ 0.1 wt. %.

The invention claimed is:
 1. A process for the manufacture of afunctionalized ethylene and propylene copolymer composition comprisingthe steps of: a) copolymerizing ethylene, propylene and at least onemasked functionalized olefin monomer in the presence of a catalystsystem, wherein the masked functionalized olefin monomer is a reactionproduct of a functionalized olefin monomer represented by the structureaccording to Formula (I) and a masking agent:

wherein R², R³, and R⁴ are each independently selected from the groupconsisting of H and hydrocarbyl with 1 to 16 carbon atoms, whereinR⁵—[X—(R⁶)_(n)]_(m) is a polar functional group containing one ormultiple heteroatom containing functionalities X—(R⁶)_(n) wherein X isselected from —O—, —S— or —CO₂— and R⁶ is H, and n is 1, or X is N andR⁶ is each independently selected from the group consisting of H and ahydrocarbyl group with 1 to 16 carbon atoms, and n is 2, wherein R⁵ iseither —C(R^(7a))(R^(7b))— or a plurality of —C(R^(7a))(R^(7b))— groups,wherein R^(7a), and R^(7b) are each independently selected from thegroup consisting of H or hydrocarbyl with 1 to 16 carbon atoms and R⁵comprises 1 to 10 carbon atoms, wherein R³ and R⁵ may together form aring structure that is functionalized with one or multiple X—(R⁶)_(n),where X is attached to either a main chain or side chain of R⁵, where mis an entire number between 1 and 10, and b) treating a product obtainedby step a) with a Brønsted acid solution, optionally containing metalsalts or ammonium salts, to abstract a residue derived from the maskingagent and combining an obtained functionalized ethylene and propylenecopolymer with a cross-linking enhancing agent selected from the groupconsisting of polyols, polyamines, polyacids, polyethers, polyesters,polycarbonates, polyamides, polyurethanes, polyureas, polysaccharides,polypeptides and combinations of at least two of said cross-linkingenhancing agents, wherein said cross-linking enhancing agent has atleast two functionalities, wherein an amount of the cross-linkingenhancing agent is from 0.01 to 10 wt %, based on a combined weight ofthe functionalized ethylene and propylene copolymer and thecross-linking enhancing agent.
 2. The process according to claim 1,wherein in step a) an ethylene to propylene weight ratio is from 20:80to 70:30.
 3. The process according to claim 1, wherein thefunctionalized olefin monomer is selected from the group consisting ofallyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1,2-diol,5-hexene-1-ol, 5-hexene-1,2-diol, 7-octen-1-ol, 7-octen-1,2-diol,9-decen-1-ol, 10-undecene-1-ol, 5-norbornene-2-methanol, 3-butenoicacid, 4-pentenoic acid or 10-undecenoic acid.
 4. The process accordingto claim 1, wherein an amount of the at least one masked functionalizedolefin monomers in step a) is from 0.01 to 30 mol %, with respect to atotal molar amount of ethylene, propylene and the at least one maskedfunctionalized olefin monomers.
 5. The process according to claim 1,wherein the masking agent is selected from trialkyl aluminum complexes,dialkyl magnesium complexes, dialkyl zinc complexes or trialkyl boroncomplexes.
 6. The process according to claim 1, wherein thecross-linking enhancing agent is selected from the group consisting ofethylene glycol, glycerol, pentaerythritol, mucic acid, galactaric acid,carbohydrates, ethylene diamine, diethylene triamine, tetramethylethylene diamine, pentamethyl diethylene triamine, polyethylenimine,maleic acid, succinic acid, tartaric acid, citric acid, polyacrylicacid, poly(ethylene-co-acrylic acid), polyvinyl acetate,poly(ethylene-co-vinyl acetate), polyvinyl alcohol,poly(ethylene-co-vinyl alcohol), polyethylene oxide, polypropyleneoxide, poly(ethylene oxide-co-propylene oxide), poly(ethylenecarbonate), poly(propylene carbonate), polycaprolactone, poly(ethylenebrassylate), polylactide, polybutylene adipate, polybutylene adipateterephthalate, polyamide 6, polyamide 4,6, polyamide 6,6 andcombinations of at least two of the foregoing cross-linking enhancingagents.
 7. The process of claim 1, wherein the functionalized olefinmonomer is 3-buten-1-ol, 3-buten-2-ol, 10-undecen-1-ol, 4-pentenoicacid, or 10-undecenoic acid.
 8. The process according to claim 1,wherein an amount of the at least one masked functionalized olefinmonomers in step a) is from 0.02 to 20 mol % with respect to a totalmolar amount of ethylene, propylene and the at least one maskedfunctionalized olefin monomers.
 9. The process according to claim 1,wherein the amount of the at least one masked functionalized olefinmonomers in step a) is from 0.05 to 10 mol % with respect to a totalmolar amount of ethylene, propylene and the at least one maskedfunctionalized olefin monomers.
 10. The process according to claim 1,wherein the masking agent is triisobutylaluminum.
 11. The processaccording to claim 1, wherein an amount of cross-linking enhancing agentis from 0.03 to 7 wt %, based on a combined weight of the functionalizedethylene and propylene copolymer and the cross-linking enhancing agent.12. A functionalized ethylene and propylene copolymer compositionobtained by the process of claim
 1. 13. The functionalized ethylene andpropylene copolymer composition of claim 12, wherein a weight ratio ofethylene to propylene in the functionalized ethylene and propylenecopolymer is from 20:80 to 70:30.
 14. The functionalized ethylene andpropylene copolymer composition of claim 12, wherein a melting enthalpyof the functionalized ethylene and propylene copolymer composition isbetween 5 J/g and 150 J/g, as measured by differential scanningcalorimetry.
 15. The functionalized ethylene and propylene copolymercomposition of claim 12, wherein the functionalized ethylene andpropylene copolymer composition comprises at least one or two types ofreversible cross-links.
 16. A thermoplastic composition comprising thefunctionalized ethylene and propylene copolymer composition of claim 12and at least one thermoplastic polymer.
 17. The functionalized ethyleneand propylene copolymer composition of claim 12, wherein the compositionis a shape memory copolymer and/or self-healing copolymer.
 18. A processfor the manufacture of a functionalized ethylene and propylene copolymercomposition comprising the steps of: a) copolymerizing ethylene,propylene and at least one masked functionalized olefin monomer in thepresence of a catalyst system, wherein the masked functionalized olefinmonomer is a reaction product of a functionalized olefin monomerrepresented by the structure according to Formula (I) and a maskingagent:

wherein R², R³, and R⁴ are each independently selected from the groupconsisting of H and hydrocarbyl with 1 to 16 carbon atoms, whereinR⁵—[X—(R⁶)_(n)]_(m) is a polar functional group containing one ormultiple heteroatom containing functionalities X—(R⁶)_(n) wherein X isselected from —O—, —S— or —CO₂— and R⁶ is H, and n is 1, or X is N andR⁶ is each independently selected from the group consisting of H and ahydrocarbyl group with 1 to 16 carbon atoms, and n is 2, wherein R⁵ iseither —C(R^(7a))(R^(7b))— or a plurality of —C(R^(7a))(R^(7b))— groups,wherein R^(7a), and R^(7b) are each independently selected from thegroup consisting of H or hydrocarbyl with 1 to 16 carbon atoms and R⁵comprises 1 to 10 carbon atoms, wherein R³ and R⁵ may together form aring structure that is functionalized with one or multiple X—(R⁶)_(n),where X is attached to either a main chain or side chain of R⁵, where mis an entire number between 1 and 10, and b) treating a product obtainedby step a) with a Brønsted acid solution, optionally containing metalsalts or ammonium salts, to abstract a residue derived from the maskingagent and combining an obtained functionalized ethylene and propylenecopolymer with a cross-linking enhancing agent selected from the groupconsisting of polyols, polyamines, polyacids, polyethers, polyesters,polycarbonates, polyamides, polyurethanes, polyureas, polysaccharides,polypeptides and combinations of at least two of said cross-linkingenhancing agents, wherein said cross-linking enhancing agent has atleast two functionalities, wherein in step a) an ethylene to propyleneweight ratio is from 25:75 to 60:40.
 19. A functionalized ethylene andpropylene copolymer composition comprising i) from 90-99.99 wt % of afunctionalized ethylene and propylene copolymer of ethylene, propyleneand at least one functionalized olefin monomer selected from the groupconsisting of allyl alcohol, 3-buten-1-ol, 3-buten-2-ol,3-buten-1,2-diol, 5-hexene-1-ol, 5-hexene-1,2-diol, 7-octen-1-ol,7-octen-1,2-diol, 9-decen-1-ol, 10-undecene-1-ol,5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid, and10-undecenoic acid; and ii) from 0.01 to 10 wt % of at least onecross-linking enhancing agent selected from the group consisting ofpolyols, polyamines, polyacids, polyethers, polyesters, polycarbonates,polyamides, polyurethanes, polyureas, polysaccharides, polypeptides,wherein said cross-linking enhancing agent has at least twofunctionalities, wherein the wt % is based on a combined weight of thefunctionalized ethylene and propylene copolymer and the cross-linkingenhancing agent.